Conversion coatings are used to promote paint adhesion and improve the resistance of painted substrates to corrosion. One type of conversion coating is a zinc phosphate conversion coating which is composed primarily of hopeite [Zn.sub.3 (PO.sub.4).sub.2 ]. Zinc phosphate coatings formed primarily of hopeite are soluble in alkali solutions. Such conversion coatings are generally painted which prevents the conversion coating from dissolving. However, if the paint coating is chipped or scratched, the zinc phosphate coating is then exposed and subject to attack by alkaline solutions such as salt water. When the conversion coating is dissolved, the underlying substrate is subject to corrosion.
In the design and manufacture of automobiles, a primary objective is to produce vehicles which have more than five-year cosmetic corrosion resistance. To achieve this objective, the percentage of zinc-coated steels used in the manufacture of vehicle bodies has continually increased. The zinc-coated steels currently used include hot-dip galvanized, galvanneal, electrozinc and electrozinc-iron coated steels. Such zinc coatings present problems relating to maintaining adequate paint adhesion. Adhesion to zinc-coated steel, uncoated steel and aluminum substrates can be improved by providing a phosphate conversion coating. To be effective in vehicle manufacturing apparitions, a conversion coating must be effective on uncoated steel, coated steel and aluminum substrates.
An improved zinc phosphate conversion coating for steel is disclosed in U.S. Pat. No 4,330,345 to Miles et al. In the Miles patent, an alkali metal hydroxide is used to suppress hopeite crystal formation and encourage the formation of phosphophyllite [FeZn.sub.2 (PO.sub.4).sub.2 ] crystal, or zinc-iron phosphate, on the surface of the steel panels. The phosphophyllite improve corrosion resistance by reducing the alkaline solubility of the coating. The alkaline solubility of the coating is reduced because iron ions from the surface of the steel panels are included with zinc in the conversion coating.
The formation of a zinc-iron crystal in a phosphate conversion coating is possible on steel substrates by providing a high ratio of alkali metal to zinc. The alkali metal suppresses the formation of hopeite crystals and allows the acid phosphate solution to draw iron ions from the surface of the substrate and bond to the iron ions in the boundary layer or reaction zone formed at the interface between the bath and the substrate. This technique for creating a phosphophyllite-rich phosphate conversion coating is not applicable to substrates which do not include iron ions.
The predominance of zinc-coated metal used in new vehicle designs interferes with the formation of phosphophyllite in accordance with the Miles patent. Generally, the zinc-coated panels do not provide an adequate source of iron ions to form phosphophyllite. It is not practical to form phosphophyllite crystals by the addition of iron ions to the bath solution due to the tendency of the iron to precipitate from the solution causing unwanted sludge in the bath. A need exists for a phosphate conversion coating process for zinc-coated substrates which yields a coating having reduced alkaline solubility.
In U.S. Pat. No. 4,596,607 and Canadian Patent No. 1,199,588 to Zurilla et al., a method of coating galvanized substrates to improve resistance to alkali corrosion attack is disclosed wherein high levels of nickel are incorporated into a zinc phosphate conversion coating solution. The Zurilla process uses high zinc and nickel levels in the zinc phosphating coating compositions to achieve increased resistance to alkaline corrosion attack. The nickel concentration of the bath, as disclosed in Zurilla, is 85 to 94 mole percent of the total zinc-nickel divalent metal cations with a minimum of 0.2 grams per liter, i.e., 200 parts per million (ppm), zinc ion concentration in the bath solution. The extremely high levels of nickel and zinc disclosed in Zurilla result in high material costs on the order of three to five times the cost of prior zinc phosphate conversion coatings for steel. Also, the high zinc and nickel levels result in increased waste disposal problems since the zinc and nickel content of the phosphate coating composition results in higher levels of such metal being dragged through to the water rinse stage following the coating stage. Reference is also made to U.S. Pat. No. 4,595,424.
It has also been proposed to include other divalent metal ions in phosphate conversion coatings such as manganese. However, one problem with the use of manganese is that it is characterized by multiple valence states. In valence states other than the divalent state, manganese tends to oxidize and precipitate, forming a sludge in the bath instead of coating the substrate. The sludge must be filtered from the bath to prevent contamination of the surface.
A primary object of the present invention is to increase the alkaline corrosion resistance of phosphate conversion coatings applied to zinc-coated metals. By increasing the resistance of the phosphate coating to alkaline corrosion attack, it is anticipated that the ultimate objective of increasing corrosion resistance of vehicles to more than five years will be achieved.
Another objective is to improve the control of the phosphate coating process so that an effective coating, which is both corrosion-resistant and adhesion-promoting, can be consistently applied to steel, aluminum and zinc-coated panels. As part of this general objective, the control of a phosphate coating process including manganese is desired wherein sludge formation is minimized.
A further objective of the present invention is to reduce the quantity of metal ions transferred to a waste disposal system servicing the rinse stage of the phosphate conversion coating line. By reducing the quantity of metal ions transferred to waste disposal, the overall environmental impact of the process is minimized. Another important objective of the present invention is to provide a conversion coating which satisfies the above objectives while not unduly increasing the cost of the conversion coating process.